The synthesis of host-guest composites consisting of entrapped strands of poly(methylmethacrylate) (PMMA) within the pores of inorganic hosts is described. Methyl methacrylate was adsorbed into microporous hosts including zeolite NaY, mordenite, beta, and ZSM-5 and then polymerized. Adsorption and polymerization was also performed in the mesoporous materials MCM-41 and MCM-48. The adsorption of methyl methacrylate (MMA) and its conversion to PMMA was followed by FTIR spectroscopy. Nitrogen sorption isotherms confirm the filling of the micro-and mesopores with the polymer. Thermogravimetry (TGA) shows that the polymer content of the composites increases with increasing pore volume, while no polymer deposition on the external host surface is detected with scanning and transmission electron microscopy. The polymers confined in the 6-35 Å diameter channels of the hosts do not show characteristic bulk behavior with respect to their glass transition temperature.

Attachment of electroactive triangular nickel clusters to gold electrodes was accomplished with 4-isocyanophenyl thiolate linkages. The disulfide linked “dimer of trimers” cluster [{Ni3(μ3-I)(μ2-dppm)3(μ3,η1-C⋮NC6H4S-)}2]2+, 5, was prepared by reaction of 2 equiv of [Ni3(μ3-I)2(μ2-dppm)3], 2, with 1 equiv of 4,4‘-bis(isocyano)diphenyl disulfide, 4. Films of [Ni3(μ3-I)(μ2-dppm)3(μ3,η1-C⋮NC6H4S-)], 6, on gold electrodes were formed by electrochemical deposition or by immersing the electrode in a methylene chloride solution of 5. After deposition, persistent oxidation and reduction of the adsorbed cluster was observed via cyclic voltammetry with peak current (i p) proportional to the scan rate. The electron acceptors methyl viologen (MV2+) and the methyl ester of cobaltocenium carboxylate [CoCpCpCOOMe][PF6] were used to demonstrate rectification in the interfacial electron transfer from nickel cluster modified gold electrodes to the electron acceptors. Surface coverage was estimated by both electrochemistry and reflection−absorption infrared spectroscopy (RAIR). Both RAIR and electrochemical measurements indicated surface coverages of cluster 6 of approximately one monolayer or 2 × 1014 molecules/cm2.